HU224664B1 - Device and method for producing silicone emulsions - Google Patents

Description

The present invention relates to apparatus and a process for preparing finely divided stable silicone emulsions, in particular emulsions of the oil-in-water type, preferably with reduced emulsifier content.

A variety of methods are known for emulsifying insoluble silicones or silanes in water. Usually, prior to actual homogenization, a small amount of water is slowly added to the finely divided silicone emulsifier to form an "water-in-oil" emulsion which is inverted when diluted with water, followed by a special oil shear emulsion. by homogenization into a finely divided emulsion. Alternatively, the silicone can be mixed with an aqueous emulsifier mixture while stirring, and the resulting coarse-grained emulsion is subjected to actual homogenization.

Depending on the process, the nature of the active ingredient (here, the silicone and silane compounds), the concentration of the emulsifier, the mixing energy introduced and, in particular, the time spent on the operation, the blended mixture may be sufficiently stable. However, most of these emulsions, also known as pre-emulsions, are coarse-grained and, due to their lack of stability, need to be immediately subjected to true homogenization. Homogenizers and Methods Ullmann's Encyclopedia of Industrial Chemistry A9. Volumes 309-310 of the 1987 edition. page. The pre-emulsion is produced in a mixing apparatus, which, depending on the nature of the connecting homogenizer, will have a decisive influence on the time.

Further processes for preparing silicone emulsions are known from EP-A-043 091 and EP-A-0 579 458. According to EP-A-043 091, a small amount of water containing all emulsifiers is added to the entire amount of silicone to form a high viscosity paste or gel which is then diluted to form the final emulsion.

The preparation of the pre-emulsion according to the classical processes becomes problematic when the siloxane and / or silane are added to the excess aqueous / emulsifier phase, especially if the silicon compounds used are monomeric, linear or optionally low molecular weight reactors with the aqueous phase or siloxane. resins diluted with compounds. These include, for example, alkyl alkoxy silanes, resins bearing alkoxy groups and optionally mixtures of the two.

A further disadvantage is that the preparation of the pre-emulsion according to known methods is very time-consuming. The siloxane component is added to the aqueous phase under stirring in a controlled manner so that the mixing is optimal. This does not allow rapid dosing.

At the beginning of the process, the first silicone molecules encounter a tremendous amount of water, which only reaches the desired concentration over time; the result is a coarse-dispersed, labile pre-emulsion which must be introduced into the homogenizer as quickly as possible.

During the addition, the water-sensitive components are not sufficiently protected from attack by the aqueous phase, even when buffered, so that the appropriate components may react with one another. This may result in difficulties with subsequent homogenization, due to the condensation processes that cause the viscosity to increase in the coarse emulsion droplets formed, and that the pre-emulsion is so unstable that it cannot be homogenized. While this error can be compensated for by drastically increasing the amount of emulsifier (in the range of about 5%), it can lead to undesirable results and environmental load for many applications.

In addition, in the case of alkyl alkoxy silanes, for example, hydrolysis and condensation reactions during emulsification render the silicone ineffective, meaning that the resulting emulsion is useless.

If the pre-emulsion is subsequently made through a paste or gel to be diluted by a separate process, low emulsion emulsions of low average droplet size may be prepared, provided that no droplet size distribution is known.

In view of the fact that many silicones exist which, at least at the required low emulsifier content, cannot be made into a satisfactory paste, the scope of the aforementioned processes is limited. In addition, certain types of emulsions, such as antifoam emulsions and emulsifier-poor (<5%), but also silicone-poor (<20%) emulsions, may not be prepared satisfactorily by the above process. For example, according to EP 0 579 458, in a very time consuming manner (see examples therein), only emulsions containing very large droplets (3-60 µm) can be obtained.

It is therefore an object of the present invention to provide a fast and thus economical process which enables the preparation of emulsions without the above drawbacks and finely divided emulsifiers with a narrow droplet size distribution but with silicone in any proportion. It is a further object of the present invention to provide an apparatus for carrying out the process. Another objective is to formulate a water stable silicone emulsion, which can be stable for many years, even from water-sensitive silicones.

Among other things, in order to ensure good reproducibility of the process, it has been particularly sought to contact the silicone in a controlled manner from the beginning to bring the amount of emulsifier required to saturate the surface of the emulsified silicone droplets in a controlled manner to harmonize the applied mechanical energy. A prerequisite for this is an emulsifier process which can be described mathematically precisely. Devices with a large influence on residence time (such as mixers) are not suitable.

Finally, it was desired that the amount of energy to be introduced would include a range that had so far been achieved only by several devices of different structures. so do2

Emulsifiers, such as antifoam emulsions, which need to be protected from high energy input, and which require multiple energy transfers through classical homogenizers, can be produced by the apparatus.

The above task has been solved by means of a system consisting of tanks, pumps and nozzles, hereinafter referred to as a mixing plant. It has been found to be particularly advantageous to connect a jet dispersant to the outlet of the mixing station. Radiation dispersants are used, for example, in the pharmaceutical and cosmetic industry for preparing dispersions (Bayer AG / EPO 101 007).

Accordingly, the present invention relates to an apparatus for preparing a silicone, silane or silicone / silane emulsion from a silicone / silicon (active ingredient) component and an aqueous phase (component) having a first mixing station for emulsion components from tanks by means of pumps; the first mixing station having a mixing unit in which the nozzles mix a jet of active ingredient with the aqueous phase to form a pre-emulsion (see Figures 1 and 2).

According to a preferred embodiment of the device according to the invention, a high pressure homogenizer is connected to the first mixing unit to receive the pre-emulsion leaving the mixing unit.

The present invention further relates to a process for the preparation of finely divided, narrow droplet size aqueous silicone and / or silane emulsions which comprises:

injecting a silicone and / or silane component into the aqueous phase containing the emulsifier in a mixing unit to form a pre-emulsion and then

- homogenize in a high-pressure homogenizer.

Emulsions containing silicone compounds and / or silanes obtained by the above process are also within the scope of the present invention.

More particularly, the present invention relates to a process for the preparation of finely divided aqueous silicone and / or silane emulsions having a U _{90 value} (i.e., narrow droplet size distribution) of less than 1.2, which process comprises:

injecting the silicone and / or silane component into the aqueous phase containing the silicone and / or silane component, while maintaining a pressure difference of less than 10 ⁶ Pa and an absolute pressure of less than 10 ⁷ Pa depending on the size of the nozzles.

- homogenizing the pre-emulsion.

The invention will be further described with reference to the accompanying drawings and embodiments. The attached drawings show

Figure 1 shows a mixing unit, a

Figure 2 schematically depicts the apparatus of the invention with a high pressure homogenizer, a

Figure 3 shows the arrangement of the nozzles of the jet dispersion, while Fig

Figure 4 illustrates a high pressure homogenizer

Figures 5, 6, 7 and 8 show the droplet size distribution of the emulsions obtained in Examples 10, 9, 18 and 19 in a differential and cumulative manner.

The expected average droplet size (d) for the apparatus of the present invention, when pressure drop (Ap) ^STR_D , emulsifier volume and surface requirement, nozzle diameter (D) ^STR_D , interfacial tension (γ), dispersed phase viscosity (η) and the number of homogenization ^steps (n) ^{STR_D is} known, can be calculated by the following formula;

d = k A (Δρ) - ° · ⁶ A η ⁰ · ⁴⁹⁵ Αγ ^θ · ³⁶⁵ AD ⁰ · ¹⁶⁵ An ⁰ · ³⁶ , where k is a constant relative to the emulsifier concentration and surface requirement.

An essential part of the mixing plant is the nozzle assembly in the M1 mixing unit, the dimensioning of which depends on the density of the two phases to be combined, their relative concentration, the pressure drop chosen and the amount of material passing through the unit.

Figure 1 illustrates a possible embodiment. For example, silicone oil 1 is injected into the aqueous phase 3 through a first nozzle 2, and the resulting mixture is stirred and homogenized vigorously in a second nozzle 4 immediately thereafter. The finite distribution is carried out in the attached STR-D beam disperser. The STR-D jet disperser can be directly connected to the unit or will only start to operate after full 5 pre-emulsions in semi-batch mode.

Nozzle system of Figure 1 is preferably operated by two (2-3) χ 10 ⁵ Pa pressure difference P1, P3 pump is fed at a rate such that if the emulsifier which, speed impact permits - the aqueous emulgeátoroldatot and silicon are combined according to the final concentrations , then pass it through the STR-D beam disperser once, twice, or up to three times.

The number of permeations generally depends on the type and amount of emulsifier. With a volume of about three percent, with one exception, one concession is enough.

Only in the case of emulsifiers which surround the surface of the silicone droplets only relatively slowly can the process be modified by dissolving all the emulsifiers in a portion of the water. In this case, a more concentrated emulsion is obtained, which can be recycled back into the aqueous emulsifier solution and then towards the nozzle, the freshly arriving silicone agent, to form a circular process. Whether or not the cycle continues for a few minutes after combining the two phases depends on the type and amount of emulsifier and the silicone to be emulsified. An additional nozzle and pump can optionally add the remaining water containing an additive, such as a thickener or preservative, to the circulating process and then transfer the resulting pre-emulsion into the STR-D jet disperser.

Figure 4 shows the STR-D jet disperser used as a 6 high pressure homogenizer. The STR-D jet disperser from 14 pumps,

EN 224 664 Β1 optionally consists of 16 vibration dampers and 18 nozzle assemblies, the latter being enlarged in Figure 3. The two-stage nozzle assembly 18 has a first nozzle 10 and a second nozzle 12 associated therewith to homogenize the pre-emulsion 5. The nozzle 10, 12 consists of an insert 11 in a tube 9, each insert having a cylindrical section 13 projecting opposite to the flow of the pre-emulsion 5 with two capillary bores 15 facing each other. The cylindrical section 13 forms a circumferential space 17 in the tube 9 and the pre-emulsion 5 flows into the tube 9, thence into the circumferential space 17 and then through the capillary holes 15 into the intermediate chamber 20. Given that the capillary bores 15 are opposed to each other, the emulsion beams exit within each other of the cylindrical portion 13, which results in particularly good dispersion. The emulsion exits the intermediate chamber 20 and enters the annular ring 22 of the nozzle 12, which it leaves through the capillary bores 24 of the nozzle 12. The finished emulsion 25 exits the STR-D jet disperser through outlet 26.

In the process according to the invention, the ratio between the total water containing the emulsifier and the silicone can also be chosen to form a gel or paste. A prerequisite for this is that the pumps used are positive displacement pumps and strong enough to transport the paste.

The process according to the invention has the advantage that it is practically continuous, takes little time and has excellent reproducibility. The process provides stable emulsions having an average droplet size of less than 1 µm at 0.5 to 3% emulsifier content. In addition, the droplet size distribution important for stability and many applications is narrower than for classical methods.

There are also some cases where an unstable emulsion is formed, but the droplet size and droplet size distribution are not important, and therefore, for cost or other reasons, subsequent homogenization of the emulsion leaving the mixing unit is neglected. The lack of stability of such an emulsion can be compensated for by increasing its viscosity by adding a neutral thickener. However, the processing of such emulsions is often poor and therefore the above method is not preferred.

Among the above mentioned emulsions there are very few high viscosity emulsions, mostly added with a high viscosity natural thickener.

Of course, it would not be economical to subsequently emulsify such an emulsion in the STR-D jet dispersant because, unless the state of the emulsion is substantially changed, the jet dispersant under the necessary process conditions cannot contribute significantly to the physical properties of the emulsion.

In the above case, it is advisable when leaving the first mixing unit emulsion is homogenized a second higher pressure, up to 10 ⁷ Pa operated pressure mixing unit.

The above method is also recommended when an easily emulsifiable silicon compound must be emulsified with an emulsifier that surrounds the surface of the silicone droplets at a satisfactory rate. In this case, no thickener is needed.

However, in order to reduce the number of machines required, it is preferable to feed the pre-emulsion from the first mixing unit to the container and then to the same mixing unit under other pressure conditions to achieve the desired degree of emulsion.

A further object of the present invention is to provide aqueous silicone and / or silane emulsions having a droplet size of about 0.4-5.0 µm, a U _{90 value} (i.e., a wide droplet size distribution), low shear force or emulsifier stabilizing emulsification. which process

- mixing unit in the silicone and / or silane component when injected into an aqueous phase containing an emulsifier pre-emulsion is prepared while maintaining a hanging nozzles dimensions of up to 10 ⁶ Pa of all the pressure differential between the two streams, 8 * of less than 10 ⁶ Pa absolute pressure drop next, then

- homogenizing the pre-emulsion in a subsequent mixing unit or over time in the same mixing unit with an absolute pressure drop of up to 10 ⁷ Pa.

Figure 2 shows an embodiment. The reference

lek meaning: VA: silicone container VB: tank of residual water (containing additive) VC: buffer tank, intermediate storage VD: buffer tank VE: storage tank, intermediate storage P1, P2: pumps (if required, positive displacement pumps) P3, P4, P5: pumps M1: water and silicone mixing nozzle STR-D: jet disperser

A low pressure VC-> P3-> M1 aqueous phase is injected into the VA-> P1-> M1-> VA silicone circuit and, at the end of the addition, the VA-> P1-> M1-> VA circuit is pressurized to in this case M1 acts as a homogenizer. The finished emulsion leaving M1 can be removed.

A prerequisite for the above is, of course, that the emulsifier should surround the droplet surface quickly enough. Otherwise, it depends not only on the emulsifier but also on the silicones which attract the emulsifier with different affinities.

Examples of silicone and silane components include:

- Silicone compounds of a standard composition:

(CH3) ₃ SiO [(CH _{3) 2} SiO] ₅₀ _ ₅ ooSi (CH3) ₃

HO (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] ₅₀ ° Si (CH ₃ ) ₂ OH (CH ₃ ) ₃ SiO [(CH ₃ ) (H) SiO] ₅₀ Si (CH ₃ ) ₃ (CH .e;

organic alkoxysilanes and their hydrolysis products, for example

CH ₃ (CH ₂ ) ₇ Si (OEt) ₃

CH ₃ (CH ₂ ) ₃ Si (OEt) ₃

HU 224 664 Β1

CH ₃ (CH ₂ ) ₁ H (CH ₂ ) ₂ ),

CH ₃ (CH ₂ ) ₇ Si (OEt) ₂ O (OEt) ₂ Si (CH ₂ ) ₇ CH ₃

CH ₃ (CH _{2) 3} Si (OEt) ₂ [O (EtO) Si (CH _{2) 3} CH _{3] 0} _ ₅ OSi (OEt) ₂ (CH _{2) 3} CH _3;

- linear organic polysiloxanes, optionally with silicon-attached reactive groups such as hydrogen, alkoxy, polyether or hydroxy and / or carbon-linked reactive groups such as polyether, amine, halogen or pseudohalogen, such as (CH ₃ ) ₃ SiO [(CH). _{3) 2} SiO] 50_ ₅₀₀ Si (CH3) ₃

HO (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] ₅₀₀ Si (CH ₃ ) ₂ OH (CH ₃ ) ₃ SiO [(CH ₃ ) (H) SiO] ₅₀ Si (CH ₃ ) ₃ (CH ₃ ) ₃ SiO [(CH ₃₎ CH ₂ = CHSi] _{3 [(CH3) 2} SiO] ₅₀ _ ₅₀₀ Si (CH3) ₃ (GH 3) 3 SiO _{[CH3 (OCH2 CH2)} gO (CH 2) 3 (CH ₃ ) SiO] ₃ [(CH ₃ ) ₂ SiO] ₆₀₀ Si (CH ₃ ) ₃ ;

branched organic polysiloxanes, optionally with silicon-linked reactive groups such as hydrogen, alkoxy, polyether or hydroxy and / or carbon-linked reactive groups such as polyether, amine, halogen or pseudohalogen, e.g.

CH ₃ Si {[(CH ₃ ) ₂ SiO] ₅₀ OSi (CH ₃ ) ₃ } ₃

CH ₃ Si {[(CH ₃ ) ₂ SiO] ₈₀ OSi (CH ₃ ) ₂ CH ₂ = CH ₃ } ₃

CH ₃ Si {[(CH ₃ ) ₂ SiO _{2 90} OSi (CH ₃ ) ₂ (CH ₂ ) ₃ (OCH ₂ CH ₂ ) ₈ OCH ₃ } ₃

H ₂ N (CH ₂ ) ₃ Si {[(CH ₃ ) ₂ SiO] ₁₈ OSi (CH ₃ )} ₃ ;

- silicone resins having alkyl groups modified with arylalkyl groups attached to the carbon atom, resins having a reactive alkoxy group, with or without a diluent, for example (θ ^ 3) ΐ, 16θ'ΐθ1,42 (CH ₃ ) ₀ , ₈ (C ₁₂ H ₂₅ ) ₀ , ₂ Si (O) ₁ (OCH ₃ ) ₁ (SiO ₂ ) ₁₀ [(CH ₃ ) ₃ SiO _1/2 ] ₀₈

SiO ₂ [(CH ₃ ) CH ₂ = CHSiO] ₀₃ [O _1/2 Si (CH ₃ ) ₃ ] ₁₂ ;

- mixtures of the above components with each other or with insoluble additives of mineral or organic origin.

The term emulsifier term refers to ionic and nonionic emulsifiers commonly used in emulsifying silicones.

Depending on the nature of the silicone or siloxane, for example, an ionic emulsifier may include:

Alkyl sulfonates having from 8 to 18 carbon atoms, optionally containing ethylene oxide or propylene oxide units;

a sulfate ester such as CH ₃ (CH ₂ ) ₆ CH ₂ O (C ₂ H ₄ O) ^ ₁₉ SO ₃ H;

alkylaryl sulfonates such as dodecylbenzene sulfonate;

quaternary ammonium compounds such as dodecyltrimethylammonium hydroxide, octyldimethylbenzylhydroxide or salts thereof.

However, nonionic emulsifiers with HLB values of 10 to 16 are preferred. If the emulsifier mixture has this HLB, the components of the mixture may have an HLB of between 2.7 and 18.7.

Nonionic emulsifiers include ethylene oxide adducts of fatty alcohols, alkylphenols, triglycerides or sugars; polyethylene oxide sorbitan laurates, palmitates, stearates; adducts of alkyl amines with ethylene oxide; and polyvinyl alcohol (e.g., mowiol), ethoxy adducts of tridecyl alcohol, ethoxy adducts of sorbitan monooleate (products of ICI Tween®), sorbitan monooleate, and mixtures thereof.

The average droplet diameter, also called droplet size, is calculated from the average volume obtained by dividing the total volume of all the droplets in the emulsion by the number of droplets.

The numerical value of the droplet size distribution width was calculated by disregarding 10% by weight (d10) of the smallest droplet volume and 10% (d90) by volume of the largest droplets, and the diameter of the largest droplet remaining in the bulk dividing the difference between the diameter of the smallest droplet by the diameter (d50) of the droplet which is less than 50% by weight of the droplets but is also greater than 50% by weight of the droplets. This numeric value is referred to below as Ug ₀ :

d90-d10 (see Figures 5, 6, 7 and 8).

Average droplet sizes were measured using Frauenhofer tilt, ultracentrifugation, or photometry based on Mie theory. Distribution curves were determined by ultracentrifugation.

The apparatus illustrated in Figure 2 as a flowchart allows the process to be variably varied according to the silicone / silane agent, emulsifier and their concentration.

Thus, for example, in the case of an easily emulsifiable material, a "fast acting" emulsifier and favorable concentrations, the silicone / silane agent (from VA) may be combined with the water / emulsifier mixture (VC) in the desired ratio in M 1, and the resulting pre-emulsion is fed directly or through a buffer vessel (VD) to the STR-D jet disperser, homogenized with a single pass, and then passed to the filling station.

The above procedure requires reliable control and synchronization of the pumps. If this is not desired and accurate adherence to the emulsifiable agent ratio is not required during M 1 mixing, but the final silicone concentration of the emulsion must be ensured, then the silicone / silane agent may be treated with water / M1. the resulting emulsion is continuously recycled to the water / emulsifier mixture (VC) and recirculated via M1 to the active ingredient. When the active ingredient is depleted, the concentration of the pre-emulsion - with the help of M1 the remaining water (from VB), is a similar process5

Add (M1- + VC- + M1) to the final value and homogenize the emulsion.

For difficult to emulsify silicone, a "slow" emulsifier or very low emulsifier concentration, the mixture may be pre-emulsified by circulating between VC and M1 before being introduced into the jet dispersant.

If a paste or gel is desired and the silicon compound is suitable, the latter is combined with a small amount of water (from VC) containing the total amount of emulsifier in the mixing unit M1, and the resulting emulsion is recycled as described above to VC and re-injecting the silicon compound in M1 to form a high viscosity pre-emulsion which, depending on the parameters chosen, may be paste or gel.

Depending on its intended use, the emulsion may be packaged as such or further processed as detailed below.

Prior to homogenizing the emulsion in the STR-D jet dispersant, it is passed through a mixing unit M1, whereby residual water (from VB), optionally containing a thickener and other additives, is injected through a nozzle to achieve the calculated composition.

If it is not sufficient to pass the emulsion through the jet disperser once, pass the emulsion around the VE - + STR-D line and pass the emulsion a second time.

If multiple permeability is desired, the emulsion from VD buffer tank through the STR-D radial disperser into the VE storage tank is permeable to 1st, while the second follows the VE-> STR-D-> VD path and so on.

In the examples below, unless otherwise stated, the partial and percentage data are by weight.

Abbreviations used:

Me: methyl et: ethyl octene: C ₈ H ₁₇ Si (OEt) ₃ V: pre-emulsion

In the tables, only the time required to prepare the pre-emulsion is given, since the time required to prepare the water / emulsifier mixture is practically the same for the present invention and the non-present invention. The actual homogenization step was also not included in the time calculation, since the time required is largely dependent on the equipment used.

In the tables, examples of the present invention are shown in bold and comparative examples are in italics.

Examples

A) Resin Emulsions

Example 1 (Comparative Example)

238.7 g of distilled water was heated to 60 ° C in a 2 liter flask, followed by stirring with 55 g (2.5% w / w of total emulsifier) (melted mixture of POE-stearyl alcohol and POE-cetyl alcohol, total HLB-). value 15.5) was added.

To the mixture, cooled to 40 ° C, was added 1447.6 g of a solution of lsopar®-G having a viscosity of 80% (CH ₃ ) ₁₁₆ Si ₁ O _{142 with an} average viscosity of 1620 mPa s at 250-400 rpm for one hour. . After about 400 rpm post-mixing was carried out for 10 minutes. An aqueous solution of 1.76 g of carboxymethylcellulose (Walocel CRT 5000 GA) in 458.7 g of water was added with stirring, followed by stirring for a further 40 minutes.

The pre-emulsion was homogenized by passing through a classical high-pressure Graulin homogenizer six times at a pressure drop of ΔΡ = 250 * 10 ⁵ Pa. The results are shown in Table 1.

Example 2 (Comparative Example)

Example 1 was repeated with 3.00% total emulsifier. The results are shown in Table 1.

Example 3

The formulation of Example 1, however, was increased by a factor of 2.7273 but with a 2.2% emulsifier mixture. 645.0 g of distilled water in the VC intermediate tank (see Figure 2) were heated to 50 ° C, followed by stirring with 133 g (2.20% w / w) of emulsifier (POE-stearyl alcohol and POE-cetyl). molten alcohol, total HLB value 15.5) was added. The mixture was pressed through pump P3 at 3 x 10 ⁵ Pa through a mixing unit M1 (nozzle diameter 2.1 / 1.0 mm) into the VC intermediate tank and kept on a circuit P3->M1-> VC for 30 seconds. To this cycle, 3948 g of resin of Example 1 was fed from the drug reservoir VA over 17 minutes at 5 x 10 ⁵ Pa using pump P1 in the mixing unit M1. The cycle was maintained for 10 minutes, and then a solution of 4.8 g of carboxymethylcellulose (Walocel CRT 5000 GA) in water (1264.2 g) was added from the VB tank containing the diluted water to the mixing unit M1 for 9 minutes. After the addition was complete, the cycle was maintained for another 40 minutes, after which the pre-emulsion was passed through the STR-D jet dispersant (nozzle diameter 0.2828 mm) three times under pressure drop of ΔΡ = 250 * 10 ⁵ Pa. The results are shown in Table 1.

Example 4

Example 3 is repeated with a total emulsifier of 2.5%. The results are shown in Table 1.

Example 5

Example 3 is repeated with a total emulsifier of 2.8%. The results are shown in Table 1.

Example 6

Example 3 was carried out using a total emulsifier of 3.0%. The results are shown in Table 1.

HU 224 664 Β1

Table 1

Example / átengedé- sek Droplet diameter (pm) Stability (months) Example 1 (Comparative) pre-emulsion > 5,000 0 Release 1 4.954 / Release 2 4.687 0.5 3. assignment 4.423 0.5 4. assignment 4.343 0.5 5th assignment 4.216 0.5 Release 6 4.094 0.5 Example 2 (Comparative) pre-emulsion > 5,000 0 Release 1 4.760 / Release 2 4.487 0.5 3. assignment 4.390 0.5 4. assignment 4.202 0.5 5th assignment 4.068 0.5 Release 6 3.989 0.5 Example 3 (according to the invention) pre-emulsion > 5,000 0 Release 1 2.915 / Release 2 2,143 > 6 3. assignment 1.617 > 6 Example 4 (according to the invention) pre-emulsion > 5,000 0 Release 1 2,550 / Release 2 0.653 > 6 3. assignment 0,642 > 6 Example 5 (according to the invention) pre-emulsion 5,000 0 Release 1 2.453 / Release 2 0.660 > 6 3. assignment .593 > 6 Example 6 (according to the invention) pre-emulsion > 5,000 0 Release 1 2.106 / Release 2 0.634 > 6 3. assignment 0.589 > 6

B) Resin / Silane Emulsions (Water Sensitive Emulsions)

Example 7 (Comparative Example) g emulsifier mixture (1.0% w / w total) (ethoxylated sorbitan monolaurate / ethoxylated oleyl alcohol, total HLB 15.3), 816.22 g water and 2.18 g of diethanolamine was stirred in a 4 liter mixing vessel at 80 ° C for 2 hours.

A clear solution was formed. To the cooled solution, at 700 rpm, 49.2% octyltriethylsilane and 50.8% (CH ₃ ) q 0 ((- ^ 12 ^ 25) 0 2θΚθ) ι (θθ ^ 3) ι 1359.6 g of a mixture of the resin composition were added. After the addition was complete, stirring was continued at 550 rpm for a further 30 minutes. A sample was taken to determine droplet size. The pre-emulsion was homogenized twice with a Gaulin classical homogenizer at a pressure drop of ΔΡ = 250Ρ10 ⁵ Pa. The results are shown in Table 2.

Example 8

A double formulation of Example 7 was used. 44 g of emulsifier mixture (1.0% based on the total amount) (mixture of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol, total HLB 15.3), in a VC intermediate tank (see Figure 2), 1632.44 g water and Diethanolamine (4.36 g) was added and the mixture was stirred at 80 ° C for 2 hours. A clear solution formed by the körbeszivattyúztunk Buildings mobile>P3-> M1- »VC circle over ⁵ minutes at 3χ10 Pa after cooling. During this process the VA szilikontartályból through the pump P1 and M1, the mixing unit (nozzle diameter 2.1 / 1.0 mm) for 3.5 min, 49.2% of octyl triethoxy silane and 50.8% (CH ₃₎ O, _{8 (C12} H25) o, added 2 Si (0) ₁ (OCH _{3) 1} resin mixture composed of 2719.2 g with 5 ^χ 10 ⁵ Pa pressure. Upon complete addition, the above cycle is still maintained for 15 minutes at ⁵ psi 3χ10. After 5 and 15 minutes, samples were taken to determine droplet size. The pre-emulsion was homogenized by two passes under a pressure drop of ΔΡ = 10 ⁷ Pa. The results are shown in Table 2.

Example 9 (Comparative Example) g emulsifier mixture (1.0% w / w total) (ethoxylated sorbitan monolaurate / ethoxylated oleyl alcohol, total HLB 15.3), 163.2 g water and 2.18 g of diethanolamine was stirred in a 4 liter mixing vessel at 80 ° C for 2 hours. A clear solution was formed. 49.2% octyltriethoxysilane and 50.8% (CH ₃ ) _{0 8} (C ₁₂ H ₂₅ ) _{0 2} SiO) were added to the cooled solution at 700 rpm in 65 min. 1359.6 g of a mixture of (OCH ₃ ) ₁ resin were added. After the addition was complete, stirring was continued at 550 rpm for a further 30 minutes. A viscous paste was formed. At the specified speed, 653.0 g of water were added to the paste over a period of 30 minutes and the mixture was stirred until the droplet size fell below 5 pm (45 minutes). The pre-emulsion was homogenized twice with a Graulin classical homogenizer at a pressure drop of ΔΡ = 2χ10 ⁷ Pa. The results are shown in Table 2.

Example 10

Three times the formulation of Example 9 was used. For 66 g of emulsifier mixture (1.0% of total volume) (mixture of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol, total HLB value 15.3) in VC intermediate container (see Figure 2)

HU 224 664 Β1

Water (489.60 g) and diethanolamine (6.54 g) were added and the mixture was stirred at 80 ° C for 2 hours. A clear solution was formed, which was cooled and pumped for one minute at 3 x 10 ⁵ Pa over the VC->P3->M1-> VC circuit. In this cycle, 49.2% octyltriethoxysilane and 50.8% (CH ₃ ) _{0 from} the silicone vessel VA through pump P1 and mixer M1 (nozzle diameter 2.1 / 1.0mm) over 5 minutes. (C ₁ 2H25) p 2 Si (0) ₁ (OCH _{3) 1} resin composition was added a mixture of 4078.8 g with 5 x 10 ⁵ Pa. Upon completion of the addition, the above cycle was maintained at 3 x 10 ⁵ Pa for a further 4 minutes. Subsequently, 1959 g of water from VB was passed through the M1 mixing unit to the above circuit for 10 minutes. At the end of the addition, the pre-emulsion was homogenized for another 1 minute in the cycle, sampled to determine droplet size, then homogenized twice by passing through the jet dispersant at a pressure drop of ΔΡ = 10 ⁷ Pa. The results are shown in Table 2.

Table 2

Example / unbundled Pressure drop ΔΡ (10 ⁵ Pa) Droplet diameter (pm) Pre-emulsion time-consuming (minutes) Distribution width Ugo Example 7 (Comparative) pre-emulsion 0 > 5,000 95 Release 1 250 1,766 2.03 Release 2 250 0.707 1.32 Example 8 (according to the invention) pre-emulsion 3/5 3.773 * 20 Release 1 100 .647 1.21 Release 2 100 .609 1.02 Example 9 (Comparative) pre-emulsion 0 4.241 110 Release 1 200 0.763 1.75 Release 2 200 0.548 1.21 Example 10 (according to the invention) pre-emulsion 3/5 4.371 21 ** Release 1 100 0.632 1.21 Release 2 100 .583 1.10

* double quantity ** triple quantity

Example 11 for g emulsifier mixture (0.64% w / w) (mixture of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol, total HLB 15.3) in VC intermediate container (see Figure 2) Water (390.83 g) and diethanolamine (3.17 g) were added and the mixture was stirred at 80 ° C for 2 hours. A clear solution was formed, which, after cooling, was pumped at 3 x 10 ⁵ Pa for one minute through the VC → P3 → M1 → VC circuit. In this cycle, 49.2% octyltriethoxysilane and 50.8% 60 (CH ₃ ) _0/8 (C ₁₂ ) from the VA silicone vessel via pump P1 and mixer M1 (nozzle diameter 1.8 / 0.9 mm) over 3 minutes. H ₂ O ₂₅ g of a mixture of ₂ Si (O) ₁ (OCH ₃ ) ₁ resin (1980 g) was added at 5 x 10 ⁵ Pa. After the addition was complete, the above cycle was maintained for 2 minutes at 3 x 10 ⁵ Pa. Subsequently, 2594 g of water from the VB tank were added to the circuit through the M1 mixing unit for 13 minutes. At the end of the addition, the pre-emulsion was pre-homogenized for another 4 minutes in the above cycle, sampled to determine droplet size, then homogenized twice by passing through a jet dispersion at a pressure drop of ΔΡ = 95 x 10 ⁵ Pa. The results are shown in Table 3.

HU 224 664 Β1

Table 3

shared access ΔΡ pressure drop (10 ⁵ Pa) Droplet diameter (pm) Pre-emulsion time-consuming (minutes) My Emulsifier Drink (%) emulsion (months) pre-emulsion 3/5 4.326 25 0.64 - Release 1 95 0.621 > 6 Release 2 95 .611 > 6

C) Silicone oil emulsions

Example 12

To 150 g of melted emulsifier mixture (3 wt% based on total amount) (mixture of ethoxylated triglyceride and ethoxylated tridecyl alcohol, total HLB value 13.5) was added 1850 g of water at 50 ° C in a VC vessel (see Figure 2). The mixture was pumped at 3 x 10 ⁵ Pa for 2 minutes on the VC->P3->M1-> VC circuit. After cooling, 3000 g of diorganosiloxane having a viscosity of η = 350 mPa s was added to the circuit from the VA vessel via pump P1 over 18 minutes through a mixing unit M1 (nozzle diameter 1.4 / 0.7 mm) at 5 * 10 ⁵ Pa. Subsequently, the emulsion was homogenized in a STR-D jet disperser under a pressure drop of 250 x 10 ⁵ Pa. The results are shown in Table 4.

Example 13

For 200 g of melted emulsifier mixture (4% w / w of osmol) (mixture of ethoxylated triglyceride and ethoxylated tridecyl alcohol, total HLB 15.4) in VC container (see Figure 2) at 1550 g water was added and the mixture was pumped at 3 x 10 ⁵ Pa for 2 minutes (nozzle diameter 35 1.4 / 0.7 mm). After cooling at 5 x 10 ⁵ Pa was added in 5.5 min circulated through the tank VA M1 mixing unit (nozzle diameter 2.1 / 1.0 mm) with the pump P1 in 1750 g of η = 350 cps viscosity diorganopolisziloxánt. After the addition was complete, the mixture was heated under a pressure of 3 x 10 ⁵ Pa for another 5 minutes. Subsequently, 1500 g of water were added from the VB vessel under a pressure of 5 x 10 ⁵ Pa over a period of 8 minutes through the mixing unit M1. After another 5 min of circulating pump (3 x 10 ⁵ Pa), the emulsion was homogenized in a STR-D jet disperser with a pressure drop of 250 x 105 ⁵ Pa. The results are shown in Table 4.

Example 14

1240 g of water for 180 g of melted emulsifier mixture (4.5% by weight based on total amount) (mixture of ethoxylated triglyceride and ethoxylated tridecyl alcohol, total HLB value 15.4) at 50 ° C at 50 ° C was added and the mixture was pumped at 3 x 10 ⁵ Pa for 1 minute in the VC->P3->M1-> VC circuit. After cooling, 800 g of diorganopolysiloxane with a viscosity of η = 350 mPa.s was added to the circuit from the VA vessel via pump P1 over 1.5 minutes through a mixing unit M1 (nozzle diameter 2.1 / 1.0 mm) at 5 x 10 ⁵ Pa. After the addition was complete, the mixture was kept under continuous circulation at 3 x 10 ⁵ Pa for 2 minutes. Subsequently, 1780 g of water were added from the VB vessel under a pressure of 5 x 10 ⁵ Pa over a period of 8.5 minutes through the M1 mixing unit. After another 2 minutes of circulating pump (3 x 10 ⁵ Pa), the emulsion was homogenized in a STR-D jet disperser under a pressure drop of 200 x 10 ⁵ Pa. The results are shown in Table 4.

Example 15 (Comparative Example) To a melted emulsifier mixture (4.5% w / v) (mixture of ethoxylated triglyceride and ethoxylated tridecyl alcohol, total HLB value 15.4) was added 620 g of water at 50 ° C in a stirred vessel. the mixture was stirred for 3 minutes. After cooling, 400 g of diorganopolysiloxane with a viscosity of η = 350 mPa s was added via a dropping funnel over 13 minutes. Upon completion of the addition, stirring was continued at 400 rpm for another 5 minutes, followed by 27 minutes at 300 rpm (strong foaming), 890 g of water was added. The pre-emulsion was passed through a Gaulin classical homogenizer twice at ΔΡ = 200 * 10 ⁵ Pa. The results are shown in Table 4.

Table 4

Example / unbundled Droplet size (pm) Pre-emulsion time-consuming (minutes) Active ingredient concentration (%) Emulsion stability (months) Example 12 ¹ ) (according to the invention) pre-emulsion - 18 60 - Release 1 1.0 60 > 6 Release 2 0.9 60 > 6 3. assignment 0.8 60 > 6

HU 224 664 Β1

Table 4 (continued)

Example / unbundled Droplet size (pm) Pre-emulsion time-consuming (minutes) Active ingredient concentration (%) Emulsion stability (months) Example 13 ^{1 2} * (according to the invention) pre-emulsion - 23.5 35 - Release 1 0.960 35 > 6 Release 2 0.832 35 > 6 3. assignment 0.787 35 > 6 4. assignment .777 > 6 Example 14 ³ * (according to the invention) pre-emulsion - 14 20 - Release 1 2.743 20 6 Release 2 0.910 20 6 3. assignment 0.822 20 6 4. assignment .798 6 Example 15 ⁴ ) (Comparative Example) pre-emulsion - 45 20 - First 3.411 20 - Second 3.317 20 - Third 2,534 20 <6 4th 2,406 <6 2.362 <6 2,254 <6

For Table 4:

¹ > Total amount 5000 g ² ) Total amount 5000 g ³ ) Total amount 4000 g ⁴ > Total amount 2000 g

Example 16

2800 g water, 4.6 g hydrochloric acid (37%), 5.25 g glycine, 51.3 g glycerol, 200 g alkylbenzyl ammonium bromide, 30 g

A mixture of 11.4 HLB-ethoxylated tridecyl alcohol and 22.6 g glycol was charged into the VC container (see Figure 2) and pressurized to 3 x 10 ⁵ Pa over the VC ^ P3->M1-> VC circuit for 30 seconds. körbeszivattyúztuk. Thereafter, organopolysiloxane containing 2056 g of hydrogen, having a viscosity of η = 40 mPa s, was added to pump P1 via the mixing unit M1 (nozzle diameter: 1.8 / 0.9 mm) over the course of 100 seconds. At the end of the addition, the pre-emulsion was pumped into the VD buffer tank and then, with a short time delay, pumped into the STR-D jet disperser and homogenized at a pressure drop of ΔΡ = 250χ10 ⁵ Pa. The results are shown in Table 5.

Table 5

Example / áten- witnessed neither Droplet diameter (pm) Time (minutes, seconds) Stability (months) 16 / pre- emulsion 2Ί0 " Release 1 .368 4'40 " > 6 Σ 6’50 ”

D) Silicone emulsions in the mixing unit

Example 17

96.6 g of 11.4 HLB ethoxylated tridecyl alcohol, 60 552.72 g of poly (dimethylsil10) having a viscosity of η = 500 mPa s

EN 224,664 Β1 loxane), a mixture of 994.84 g of mineral oil (boiling range 382-432 ° C) and 691.04 g of di (2-ethylhexyl) phthalate from a pressure vessel of 3 x 10 ⁵ Pa for one minute. pumped into the circuit VA->P1->M1-> VA (nozzle diameter; 1.4 / 0.6 mm). Subsequently, 464.52 g of water was prepared, 0.28 g of benzyl alcohol monohemiformál (3.5-4) * 10 ⁵ Pa pressure in addition to the above was injected into the circulated line Buildings mobile>P3-> M1 3 minutes. After the addition was complete, the mixture was pumped for an additional 3 minutes at 3 x 10 ⁵ Pa over the VA->P1->M1-> VA circuit. The cycle was maintained at 12 x 10 ⁵ Pa for another 10 minutes. A dense flow stable emulsion was formed. The results are shown in Table 6.

Table 6

Time (minutes) drop Size 0 (pm) Viscosity (MPa.s) Stability (months) 17 1,748 2670 > 6

Example 18 (according to the invention)

A solution of 171.9 g of 18.1 HLB ethoxylated triglyceride and 148.1 g of 11.4 HLB ethoxylated tridecyl alcohol in 800 g of water in a VC > P3 > 2800 g of poly (dimethylsiloxane) having a viscosity of η = 1000 mPa s were injected through the drug cycle. In so doing, the drug during the initial absolute pressure of 5 * 10 ⁵ Pa to 12 * 10 ⁵ Pa was increased to 9 minutes. The pressure of the VC->P3-> M1 cycle - always 2 * 10 ⁵ Pa lower - followed this increase. Within a total of 12 minutes, the addition of siloxane was completed and a viscous white paste was formed which was pumped under a pressure of 10 x 10 ⁵ Pa and cooled on the VC → P3 → M1 circuit for a further 14 minutes.

Subsequently, 4080 g of water were injected from the VB vessel at 25 DEG C. using a P2 pump at a pressure of 12 x 10 ⁵ Pa for about 5 minutes. With increasing dilution, the pressure in the VC->P3-> M1 circuit was reduced to 4.5 * 10 ⁵ Pa, while the pressure in the P2 pump was 2 * 10 ⁵ Pa higher. Upon completion of the water addition, the pressure of the VC->P3-> M1 circuit was raised to 80 * 10 ⁵ Pa and the emulsion was discharged through the M1 mixing unit. A low viscosity, stable emulsion was formed. The results are shown in Table 7.

Example 19 (according to the invention)

A solution of 171.9 g of 18.1 HLB ethoxylated triglyceride and 148.1 g of 11.4 HLB ethoxylated tridecyl alcohol in 800 g of water in a VC>P3-> M1 cycle is prepared using VA->P1-> M1- 2800 g of poly (dimethylsiloxane) having a viscosity of η = 350 mPa s were injected through the drug cycle. In so doing, the drug during the initial absolute pressure of 7 x 10 ⁵ Pa to 10 * 10 ⁵ Pa was raised to 6 minutes. The pressure of the VC->P3-> M1 cycle - always 2 * 10 ⁵ Pa lower - followed this increase. Within a total of 6 minutes, the siloxane addition was complete, and a viscous white paste was formed which was pressurized with 10 x 10 ⁵ Pa under cooling.

VC- »P3-» M1 was pumped for another 20 minutes.

Subsequently, 4080 g of water were injected from the VB vessel at 25 ° C under a pressure of 10 x 10 ⁵ Pa at 25 ° C. With increasing dilution, the pressure in the VC->P3-> M1 circuit was reduced to 4 * 10 ⁵ Pa, while the pressure in the P2 pump was 2 * 10 ⁵ Pa higher. Upon completion of the water addition, the pressure of the VC->P3-> M1 circuit was raised to 80 * 10 ⁵ Pa and the emulsion was discharged through the M1 mixing unit. A low viscosity, stable emulsion was formed. The results are shown in Table 7.

Table 7

Example number Time (minute) Droplet size 0 ( _M m) Ugo Stability (hóna- spider) 18 32 0.689 1.541 > 6 19 32 0.531 1,168 > 6

PATENT CLAIMS

Claims (17)

An apparatus for preparing silicone and / or silane emulsions from a silicone and / or silane containing active ingredient component and an aqueous phase, comprising a first mixing station for emulsion components arriving from tanks (VA, VB, VC) by means of pumps (P1, P2, P3), that - the first mixing station having a mixing unit (M1) having nozzles (2, 4) for mixing the jet of the active ingredient with the aqueous phase (3) into a pre-emulsion (5), - the distance between the nozzles (2, 4) is 1 to 10 times the diameter of the second nozzle (4), preferably 2 to 4 times, - the second nozzle (4) having a diameter of about 2 to 3 times the diameter of the first nozzle (2), and - a jet dispersant (6) coupled to the mixing station for receiving the pre-emulsion (5) exiting the mixing station, and the pressure drop in the jet dispersant (STR-D) is between 2 * 10 ⁵ Pa and 10 ⁸ Pa, preferably between 5 * 10 ⁵ Pa and 6 * 10 ⁷ Pa, and - an intermediate tank (VD) serving as a buffer tank is connected to the mixing unit (M1) and the pre-emulsion (5) is introduced into the jet disperser (6) via the intermediate tank (VD). Apparatus according to claim 1, characterized in that the mixing station comprises a pre-homogenizing unit (VC, P3) in which the pre-emulsion can be pre-homogenized in a circular process. Apparatus according to claim 1 or 2, characterized in that a dilution device (VB, P2) is located in front of the mixing station and the jet disperser (6). HU 224 664 Β1 4. Apparatus according to any one of claims 1 to 3, characterized in that the mixing unit (M1) consists of two successively arranged nozzles (2, 4). Apparatus according to claim 4, characterized in that the pressure difference between the nozzles (2,4) of the mixing unit (M1) is between 10 ⁵ Pa and 10 ⁶ Pa, preferably 2 * 10 ⁵ Pa and 3 * 10 ⁵ Pa. 6. Apparatus according to any one of claims 1 to 5, characterized in that the first nozzle (2) of the mixing unit (M1) injects the spray jet (1) into the aqueous phase (3) and the second nozzle (4) the spray jet (1) with the aqueous phase (3) ) intensively mixing and homogenizing nozzle. 7. Apparatus according to any one of claims 1 to 4, characterized in that the jet dispersant (STR-D) consists of a plurality of nozzles (10, 12) arranged in a row. 8. Apparatus according to any one of claims 1 to 3, characterized in that the absolute pressure drop due to the formation of the mixing plant is between 2 * 10 ⁵ Pa and 10 ⁷ Pa, preferably 2 * 10 ⁵ Pa and 6 * 10 ⁶ Pa. 9. In Figures 3-8. Apparatus according to any one of claims 1 to 4, characterized in that the diluent comprises a tank (VB) containing residual water and optionally an additive and a pump (P2) for adding water to the pre-emulsion by means of the first nozzle (2) of the mixing unit (M1). 10. Apparatus according to any one of claims 1 to 3, characterized in that a storage tank (VE) is connected to the jet dispersion (6), from which the emulsion can be added to the jet dispersion (6) by means of a pump (P5). A process for the preparation of finely divided aqueous silicone and / or silane emulsions having a U ₉₀ value of less than 1.2, characterized in that the process comprises: injecting the silicone and / or silane component into the aqueous phase containing the silicone and / or silane component, while maintaining a pressure difference of less than 10 ⁶ Pa and an absolute pressure of less than 10 ⁷ Pa depending on the size of the nozzles. - homogenizing the pre-emulsion in a ray dispersant, whereby U _{90 is} defined by U ₉₀ = (d90-d10) / d50, where d10 and d90 are the smallest droplet diameter (d10) and the largest droplet diameter (d90) in the set remaining after subtracting 10% by weight of the smallest droplet droplets and 10% by weight of the largest droplets, while d50 is the diameter of the droplet which is less than 50% by weight of all droplets, however, it is greater than 50% by weight of all drops. 12. The method of claim 11, characterized in that the homogenization is carried out by jet disperser up to 10 ⁸ Pa in pressure drop. 13. The process of claim 12, wherein the pre-emulsion leaving the mixing unit is introduced directly or through a buffer tank into the jet dispersant. 14. The process of claim 12, wherein the pre-emulsion is pre-homogenized at the mixing plant in a circular manner and then introduced into the jet dispersant. 15. The process of claim 13, wherein the pre-emulsion is homogenized in a circular fashion with less water than required, then introduced into the jet dispersant, optionally inverted and diluted with water to the desired concentration. 16. The process of claim 13, wherein the pre-emulsion is homogenized in a circular fashion with less water than required, then adjusted to the desired concentration by dilution with water in a downstream diluent and then introduced into the jet dispersant. A process according to claim 14 or 15, wherein the diluent comprises a thickener.